JPS6031521A - Heat-resistant molding resin composition - Google Patents

Abstract

PURPOSE:The titled composition having excellent heat resistance, heat insulation, and mechanical properties, especially slidability to soft metals, and good workability and moldability and useful as a sliding material, friction material, or the like, prepared by adding a specified composite filler to a specified thermosetting resin. CONSTITUTION:The titled composition comprising 30-70wt% thermosetting resin essentially consisting of a polymaleimide of formula I , an aminophenol of formula II, and an epoxy compound having at least two epoxy groups on the molecule and 70-30wt% composite filler containing 50-83wt% fluorocarbon resin and 38-5wt% benzoguanamine/formaldehyde condensate. In the above formulas, R<1> is an n-valent organic group, X<1>, X<2>, and R<2> are each H, a halogen, or a monovalent organic group, n>=2, and m is 1-5. This composition has excellent heat resistance, heat insulation, and mechanical properties, especially slidability to soft metals such as Al and brass, and good workability and is useful as a sliding material, friction material, electrical insulating material, or the like.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a molding product that has good heat resistance, heat insulation, and mechanical properties, and in particular has a sliding property of 10 on soft metals such as aluminum and brass. The present invention relates to a heat-resistant resin composition.

[Technical background of the invention and its problems] Asbestos 11 has been used as a base material for molding materials and friction materials with excellent heat insulation properties. However, the use of asbestos is now prohibited as it is considered harmful. Regarding sliding properties, carbon U and fiber are effective against hard metals such as steel, but aluminum
Even carbon fibers have the problem of large amounts of wear and poor sliding properties against soft metals such as brass. Furthermore, as binder resins, thermosetting phenolic resins and epoxy resins are the mainstream, but they have poor heat resistance and there is a limit to their use in high-angle multi-stripes (4).

Ll aspect 1 of the invention The present invention has been made in view of the above-mentioned drawbacks, and is a heat-resistant resin composition for molding that has excellent heat resistance, heat insulation properties, mechanical properties, and sliding properties on soft metals. is intended to provide.

[Summary of the Invention] As a result of intensive research aimed at achieving the above object, the present invention has revealed that excellent results can be obtained as a molding resin composition by using a composite filler such as a thermosetting resin described below. There is a heading C.

That is, the present invention is based on the general formula (A) <a> (wherein R1 is an n-valent organic group, and x' and x2 are the same or different monovalent atoms selected from a hydrogen atom, a halogen atom, or an organic group, or (b) General formula (wherein R2 is a monovalent atom or group selected from a hydrogen atom, a halogen atom, or an organic moiety); , m represents an integer of 1 to 5, respectively), and (C) an epoxy compound containing two or more epoxy y:4 in one molecule. 30 to 70% by weight of thermosetting resin as a component, (B) 50 to 83% by weight of fluororesin and 38 to 5% by weight.
% of a benzoguanamine formaldehyde condensate, and 70 to 30% by weight of a composite filler.

One of the essential components of the thermosetting resin used in the present invention is C (
A> The polymaleimides in (a) include ethylene bismaleimide, 1-reemerene bismaleimide, m- or p-phenylene bismaleimide, 4.4--
Diphenylmethane bismaleimide, 4.4'-diphenyl ether bismaleimide, 4.4'-Schiff1nylsulfan bismaleimide, 4.4'-dicyclohexylmethane bismaleimide, m- or p-xylylene bismaleimide, 4.4' -Diphenylene bismaleimide, etc.

In addition, if necessary, N may be added together with these polymerimides.
-3-chlorophenylmaleimide and N-4-nitroph 1
J of nilmaleimide, less Gul of nape nonreimides
It can be used for

In addition, as the essential component (b) amine phenol, o-
, m-, or p-aminophenol, o-, m-.

or p-amine cresol, aminoxylenol containing various 16-substituted heterophenols, aminochlorophenol, amitub[j-mphenol, aminecabucol, amylzorcin, aminobis(human 1]xyphenol)propane,
Examples include aminooxybenzoic acid.

In the present invention, one or more of these polymaleimides and amine phenols are selected from each of these polymaleimides and amine phenols, and the reaction mixture is 1 to 7. The amine phenol (b) is defined as a λ1j ratio of 5 to 40 weight parts, more preferably 10 to 30 weight parts, per 100 iq) parts of the maleimide. If the amount of amine phenol is less than 5 parts by weight, the compatibility between the addition reaction product and the below-mentioned (C):C boxy compound will not be sufficient.

On the other hand, if the amount of amino enol exceeds 40 parts by weight, the amino groups become excessive and the heat resistance of the resin decreases, which is not preferable.

The reaction temperature is generally 50 to 200°C, preferably 80 to 180°C, and the reaction time can be arbitrarily selected from several minutes to several tens of hours depending on the reaction components. can.

In the present invention, examples of the epoxy compound having two or more epoxy groups in one molecule of the essential component (C) to be mixed with the addition reaction product 1!7 in this way include bisphenol A type epoxy resin, bisphenol F-type epoxy resin, novolac type Evo 4 Niji resin, polyglycidyl diester resin of polycarboxylic acid, polyglycidyl ether of polyol, urethane-modified epoxy resin, aliphatic or alicyclic polyepoxide obtained by epoxidizing an unsaturated compound, There are epoxy resins with heterocycles, epoxy resins with heterocyclic rings, epoxy resins with glycidylated amines, etc. One or two of these! ! ! ! Select and use the above.

What is the preferred blending ratio of the polymaleimide-aminophenol addition reaction product and these epoxy compounds? 1 is present, the addition reaction product is 30 to 80% by weight, and the epoxy compound is 70 to 20% by weight (preferably 1%).

If it is less than 1% by weight of 30% by weight, the heat resistance will not be sufficient, and if it exceeds 80% by weight, the heat resistance will be sufficient but the mechanical strength will decrease, which is not preferable. Within the above blending range, a thermosetting resin with good curability and moldability and excellent heat resistance can be obtained without limiting the mixing or reaction. However, usually, first, the polymaleimide (a) and the amine phenol (b) are subjected to an addition reaction to produce 1rJ of the product, and then (C) an epoxy group having two or more epoxy groups in one molecule is added to the product. A thermosetting resin is obtained by adding the compound.

Examples of the fluororesin used as one component of the composite filler used in the present invention include tetrafluoroethylene resin, fluorinated alkoxyethylene resin, 1-ethylene fluoride propylene ether 4'A resin, and 1-ethylene tetrafluoride resin. Examples include butyl hexafluoride cobylene copolymer resin, calcined Teflon powder, and the like.

Furthermore, the benzoguanamine formaldehyde condensate used as the second component of the composite filler, for example, FP-
100B (trade name manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.). Its chemical structure is as follows, and its shape is a colorless spherical fine powder.

(In the formula, k represents an integer of 2 or more.) The blending ratio of the fluororesin and benzoguanamine formaldehyde condensate of the composite filler [50-83% by weight of fluororesin, 38-83% by weight of benzoguanamine formaldehyde condensate]
Preferably, the content is 5% suspended.

If the content is less than 50% by weight of the fluororesin and less than 5% by weight of the benzoguanamine formaldehyde condensate, there is no effect on sliding properties, and if it exceeds 83% by weight and 38% by weight, heat resistance deteriorates, which is not preferable.

Furthermore, as other components of the composite filler, -C1 graphite, molybdenum disulfide, boron nitride, etc. can also be added. In particular, when heat insulation is required, graphite is not preferred, so it is added as appropriate. Mano [, as an internal l1II type agent or,
Carnauba wax, higher saturated fatty acid esters, stearic acid, zinc stearate and the like can be added depending on the number of cores.

Furthermore, if the molded article is to be colored, a pigment such as carbon black or spirit black may be added.

The heat-resistant resin composition for molding of the present invention contains 30 to 70% by weight of the above-mentioned thermosetting resin and 70 to 30% by weight of a composite filler.
However, the blending ratio of these is limited to the above range because the thermosetting resin is 30% by weight.
If it is less than 70%, the workability and moldability will be poor, and if it exceeds 70%, it will not be possible to obtain a molded product that satisfies the required properties.

Further, the resin composition of the present invention is thermosetting, and generally has a
It is cured by heating to a temperature of 50 to 250°C, but various additives may be added as necessary to further improve various properties. For example, known acid anhydrides,
Curability can be further improved by adding a curing catalyst such as boron fluoride fil1, tertiary amines, imidazoles, quaternary antnium jn, peroxides, etc.

[Effects of the invention] The heat-resistant resin composition for molding of the present invention has heat resistance, heat insulation properties,
It not only has excellent mechanical properties, especially sliding properties on soft metals such as aluminum and brass, but also has good workability and moldability, and can be used in a wide range of applications such as sliding materials, friction materials, and electrical insulation materials. .

[Embodiments of the invention] Next, the present invention will be specifically explained with reference to Examples.

Examples 1 to 6 N,N'-methylene bismaleimide, m-aminophenol, epoxy resin, and 2-ethyl-4-methylimidazole were selected at the weight composition ratio 'C- shown in Table 1, A thermosetting resin was synthesized.

A composite filler component was added to the obtained thermosetting resin in the weight composition ratio shown in Table 1, and the mixture was uniformly stirred and mixed to obtain a heat-resistant resin composition for molding.

Comparative Examples 1 to 4 Resins and resin compositions were obtained in the same manner as in the examples using the composition ratios shown in Table 1.

The resin compositions thus obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were molded at a temperature of 200 to 220°C using a pressure molding machine.
, pressure 100-300 kg/cm2, time 1-2 minutes/
Pressure molding per mm, followed by 200~230℃, 5~
After curing for 15 hours, molded articles for various tests were manufactured. The mechanical properties of this test molded article were measured according to JIS-6911.

In addition, the sliding properties were measured using a thrust type friction and wear tester using an aluminum (A5052-BD) metal with a sliding area of 2 cm' (cylindrical shape with outer diameter 25.6φ and inner diameter 20.0φ, 3S finish). Lubrication, sliding speed 1+n/sec, pressurization m 10-50kO/C11l'
(Cumulative load after 10 minutes of operation at 10 kg/Cl12) Calculate the coefficient of dynamic friction by 1. :. In addition, the sliding speed is 0.3cm
Wear m was measured after continuous operation for 24 hours under the conditions of 10 kg/cm2 and a load of 10 kg/cm2. These results are shown in Table 2.

As is clear from Table 2, it exhibits excellent mechanical properties even at high temperatures, and also exhibits sliding properties with a small coefficient of friction and little wear. It can withstand use as a molded product.

Patent applicant: Toshiba Chemical Corporation

Claims (1)

[Scope of Claims] 1 (A> (a) General formula (wherein R1 represents a zero-valent organic group, ×1°X2 represents the same or different monovalent organic group selected from hydrogen atoms, halogen atoms, or Atom or Ll
(b) General formula (wherein R2 is a monovalent atom or group selected from a hydrogen atom, a halogen atom, or an organic group, m is an integer of 1 and 5, respectively, and the addition reaction product with aminophenol shown in Table 1), and (C) an epoxy compound having two or more epoxy groups in one molecule are the essential components. 70-30% by weight of a composite filler containing 50-83% fluororesin and 38-5% benzoguanamine formaldehyde condensate; A heat-resistant resin composition for molding, characterized by: